CN109560339B - Method for pre-embedding anions and full battery - Google Patents

Method for pre-embedding anions and full battery Download PDF

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CN109560339B
CN109560339B CN201811424287.5A CN201811424287A CN109560339B CN 109560339 B CN109560339 B CN 109560339B CN 201811424287 A CN201811424287 A CN 201811424287A CN 109560339 B CN109560339 B CN 109560339B
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CN109560339A (en
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崔光磊
韩鹏献
韩晓琪
刘海胜
吴天元
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a method for pre-embedding anions, which comprises the following steps: firstly, a metal electrode is separated from an anode through a diaphragm, the metal electrode is placed in electrolyte and charged through an external power supply, the charging rate current is 0.01C-0.2C, the pre-embedded anion quantity is 1-30% of the actual maximum embedded anion capacity of the anode, and then the anode and the cathode pre-embedded with cations form a full battery in the electrolyte through the diaphragm. The full battery prepared by the method for pre-embedding anions can effectively make up for the loss of the initial charging capacity of the positive electrode, keep the full battery working on a platform all the time, and greatly improve the coulombic efficiency and the cycle performance. The method can be applied to all metal ion or metal batteries involving anion intercalation reaction, including lithium, sodium, potassium, aluminum, magnesium, zinc batteries, but not limited to the above batteries.

Description

Method for pre-embedding anions and full battery
Technical Field
The invention belongs to the field of electrochemical energy storage devices, and particularly relates to a method for pre-embedding anions and a full battery obtained by using the method.
Background
The energy crisis and environmental problems are increasing day by day, accelerating the rapid development of new energy industry. Under the current situation, environmental-friendly electrochemical energy storage technology which supplies green energy and exerts low-carbon energy conservation and emission reduction to the utmost extent is increasingly emphasized. In recent years, the development of new electrochemical energy storage devices with high operating voltages has received a great deal of attention, in particular with high-voltage LiCoO2Or Li (NiCoMn) O2And matching the anode material with the graphite cathode. However, as the market price of metal elements in lithium-containing metal oxides containing positive electrodes is increased over and over, the cost is increased.
The study finds that the anions can generate intercalation reaction in the graphite carbon material, thereby being used as a full battery consisting of the positive electrode and the graphite negative electrode material. Therefore, the double-carbon battery with the anode and the cathode made of cheap and easily available carbon materials becomes a next-generation research hotspot. However, the first intercalation process of anions has low coulombic efficiency (< 85%), consumes a large amount of anions, and if the anions and the negative electrode directly form a full battery, the internal resistance is easy to increase gradually during repeated charge and discharge, and the cycle performance is poor.
Therefore, the technical personnel in the field are dedicated to developing a method capable of improving the coulombic efficiency of the full battery, and then the full battery can be developed, so that the full battery has the characteristics of high working voltage, better cycle performance, lower cost, simple and easy preparation process and operation, and easy large-scale production, and meanwhile, the produced battery can be widely applied to the fields of electric automobiles, aerospace, deep sea submersible vehicles and the like.
Disclosure of Invention
In order to solve the existing problems, the invention provides a method for pre-embedding anions and a full battery obtained by using the method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for pre-embedding anions comprises the steps of placing a half cell consisting of a positive electrode in electrolyte, and charging through an external power supply, wherein the charging rate current is 0.01C-0.2C, and the charging amount is 1-30% of the actual maximum anion embedding capacity of the positive electrode.
The charging through the external power supply can be carried out once until the actual maximum embedded anion capacity of the anode is reached; or, the negative ion-intercalation capacity is repeatedly and continuously charged and discharged and then is recharged to the actual capacity maximum.
The multiplying current is based on the capacity that the positive electrode can actually contain anions under 1C.
The number of repeated continuous charging and discharging is 1-3.
The half cell formed by the anode sequentially consists of a metal electrode, a diaphragm and the anode; wherein the metal electrode is lithium, sodium, potassium, aluminum, magnesium or zinc.
The electrolyte is composed of anions, cations and a solvent, wherein the anions areThe compound can be hexafluorophosphate radical PF6 -Hexafluoroarsenate AsF6 -Hexafluoroantimonate radical SbF6 -BF (tetrafluoroborate) radical4 -BOB, bis (oxalato) borate-Difluorodioxooxalato borate DFOB-Bis (trifluoromethylsulfonyl) imide TFSI-Bis-fluorosulfonylimide radical FSI-Tris (pentafluoroethyl) trifluorophosphate FAP-Triflate CF3SO3 -Perchlorate radical ClO4 -One of (1);
the cation in the electrolyte may be Li+、Na+、K+、Al3+、Mg2+、Zn2+One of (1);
the solvent in the electrolyte may be Sulfolane (SL), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Propylene Carbonate (PC), Ethylene Carbonate (EC), Methyl Propyl Carbonate (MPC), gamma-butyrolactone (GBL), fluoroethylene carbonate (FEC), Ethyl Acetate (EA), ethyl Trimethylacetate (TMEA), Methyl Butyrate (MB), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Propyl Acetate (PA), Methyl Acetate (MA), ethyl acetoacetate (EAA), methyl trimethylacetate, 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide (Pyr)14TFSI);
the concentration of the electrolyte is 0.1-5 mol/L.
A full battery formed by the pre-intercalated anion positive electrode and a fresh pre-intercalated cation negative electrode in an electrolyte through a diaphragm; the pre-embedded anion positive electrode is a half-cell formed by a positive electrode and placed in electrolyte, and is charged through an external power supply, the charging rate current is 0.01C-0.2C, and the charging amount is 1-30% of the actual maximum embedded anion capacity of the positive electrode.
The manufacturing method of the positive and negative pole pieces comprises the steps of mixing an active material, a conductive agent and a binder into slurry according to the mass ratio of 90: 1-5: 1:5, coating the positive pole on an aluminum foil, coating the negative pole on a copper foil, keeping the mixture in a vacuum oven at 120 ℃ for 24 hours, and cutting the mixture into fixed shapes.
A fresh positive ion pre-intercalation negative electrode is obtained by forming a circuit by the negative electrode obtained in claim 7 and a lithium metal sheet, and intercalating lithium into the negative electrode by using a current of 0.02C, wherein the capacity of the negative electrode pre-intercalation lithium accounts for 20-50% of the maximum lithium intercalation capacity actually available for the negative electrode active material.
The negative active material is a graphite material; the binder is one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), hydroxypropyl methylcellulose (HPMC), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); the conductive agent is one or more of carbon black, graphite, graphitized carbon fiber and carbon nano tube.
The graphite material is one or more of natural graphite, artificial graphite, graphitized mesophase carbon microspheres, graphitized carbon fibers and soft carbon.
The invention has the advantages that:
compared with the prior art, the pre-embedded anion technical scheme can effectively supplement the first irreversible capacity loss of the battery, greatly improve the first charge-discharge coulombic efficiency and the long-term circulating capacity retention rate of the whole battery, and the method can be applied to all metal ion or metal batteries related to anion embedding reaction, including lithium, sodium, potassium, aluminum, magnesium and zinc batteries, but not limited to the batteries.
Detailed Description
The present invention will be further illustrated by the following examples.
Example 1:
the method for pre-embedding anions comprises the following steps:
1) and (3) manufacturing a positive plate and a negative plate: uniformly mixing and stirring the graphitized mesophase carbon microspheres, the carbon black and the binder according to the mass ratio of 85:10:5 (the mass ratio of the styrene-butadiene rubber emulsion to the sodium carboxymethylcellulose in the binder is 3.5:1.5) to form slurry, respectively coating the slurry on an aluminum foil and a copper foil to be respectively used as a positive electrode and a negative electrode, drying and cutting into a certain size.
2) Pre-intercalation of anions: in the presence of LiPF6In the electrolyte with the concentration of 1mol/L, the solvent in the electrolyte is a mixed solvent of methyl ethyl carbonate and sulfolane, and the metal lithium is used as counter currentAnd the obtained diaphragm between the positive plate and the metal lithium is a glass fiber diaphragm to form a half cell. Charging the half-cell with 0.1C rate current on the charging and discharging instrument, wherein the anion PF6 -Starting embedding into the positive electrode, discharging after reaching the upper limit voltage, continuously charging and discharging for 2 times, and performing third charging when the charging amount is the actual maximum embedding PF of the positive electrode6 -At 10% of the capacity, the charging was stopped.
3) Fresh pre-intercalated lithium ion negative electrode: in the presence of LiPF6In the electrolyte with the concentration of 1mol/L, the solvent in the electrolyte is a mixed solvent of methyl ethyl carbonate and sulfolane, metal lithium is used as a counter electrode, and the obtained diaphragm between the negative plate and the metal lithium is a glass fiber diaphragm to form the half-cell. Discharging the half-cell on a charge-discharge instrument by adopting current with 0.02C multiplying power so as to pre-embed Li+When pre-inserting Li+The amount of (A) is such that Li intercalation into the negative electrode can be maximized in practice+When the capacity is 30%, the discharge is stopped.
All-battery: PF pre-intercalating the above anion6 -The positive electrode and the prepared fresh pre-embedded lithium ion negative electrode form a full battery, a glass fiber diaphragm is adopted, and the electrolyte is LiPF with the concentration of 1mol/L6(methyl ethyl carbonate + sulfolane mixed solvent).
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery reaches 99.5%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 98.5%.
Example 2:
the difference from example 1 is that the anion pre-insertion PF was performed according to the anion pre-insertion procedure described in example 16 -The amount of (A) is the positive electrode actual maximum embedded PF6 -The balance of 1% of the capacity was the same as in example 1. As a result, it was found that: the first coulombic efficiency of the full battery is 94.5%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 88.7%.
Example 3:
the difference from example 1 is that the anion pre-insertion process described in example 1 was carried outPF pre-intercalated with anions6 -The amount of (A) is the positive electrode actual maximum embedded PF6 -The balance of 30% of the capacity was the same as in example 1. As a result, it was found that: the first coulombic efficiency of the full battery is 93.5%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 91.6%.
Comparative example 1:
all-battery: the non-pre-embedded PF of example 16 -The positive electrode and the fresh pre-embedded lithium ion negative electrode in the embodiment 1 form a full battery, and the LiPF electrolyte which is 1mol/L in the same way is adopted6(methyl ethyl carbonate + sulfolane mixed solvent).
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery is 81.3%, and after 3000 times of continuous charge and discharge, the capacity retention rate is 82.5%.
Example 4:
the difference from example 1 is that the pre-anion-intercalation process is: with 1mol/L LiPF6And (ethyl methyl carbonate + sulfolane mixed solvent) is used as electrolyte, metal lithium is used as a counter electrode, and a glass fiber diaphragm is adopted as a diaphragm between a positive electrode and the metal lithium to form the half cell. Charging the half-cell with 0.1C rate current on the charging and discharging instrument, wherein the anion PF6 -Starting to embed into the positive electrode, and charging for 1 time to the actual maximum embedded PF of the positive electrode6 -10% of the capacity, the charging was stopped.
As a result, it was found that: the first coulombic efficiency of the full battery is 98.6%, and after 3000 times of continuous charging and discharging, the capacity retention rate reaches 97.3%.
Example 5:
the difference from example 1 is that the electrolyte in example 1 is replaced by NaBF4The electrolyte with the concentration of 0.1mol/L, the solvent in the electrolyte is a mixed solvent of ethylene carbonate and diethyl carbonate, metal sodium is used as a reference electrode, and a diaphragm between a positive electrode and the metal sodium is a glass fiber diaphragm to form a half cell. Charging the half-cell with 0.1C rate current on a charging and discharging instrument, wherein the anion BF is generated6 -Begin to embed in the positive electrodeAfter reaching the upper limit voltage, the discharge is started, and after 2 times of continuous charge and discharge, the third charge is carried out, when the charge quantity is the actual maximum embedded BF of the positive electrode6 -At 10% of the capacity, the charging was stopped.
Fresh pre-intercalation of sodium ion negative electrode: NaBF at 0.1mol/L4In the electrolyte solution (mixed solvent of ethylene carbonate and diethyl carbonate), the negative electrode sheet obtained in example 1 was used, and a glass fiber separator was used between the negative electrode sheet and sodium metal to form a half cell. Discharging the half-cell on a charge-discharge instrument by adopting current with 0.02C multiplying power so as to pre-embed Na+When pre-embedding Na+The amount of (A) is that the negative electrode can practically embed Na maximally+When the capacity is 30%, the discharge is stopped.
All-battery: the pre-embedded anion BF6 -The positive electrode and the prepared fresh pre-embedded sodium ion negative electrode form a full battery, a glass fiber diaphragm is adopted, and the electrolyte is 0.1mol/L NaBF4/(mixed solvent of ethylene carbonate + diethyl carbonate).
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery reaches 99.3%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 99.1%.
Example 6:
the difference from example 1 is that the electrolyte in example 1 was changed to KPF6The electrolyte with the concentration of 0.6mol/L, the solvent in the electrolyte is propylene carbonate, the metal potassium is used as a reference electrode, and a diaphragm between the positive electrode and the metal potassium is a glass fiber diaphragm to form the half cell. Charging the half-cell with 0.1C rate current on the charging and discharging instrument, wherein the anion PF6 -Starting embedding into the positive electrode, discharging after reaching the upper limit voltage, continuously charging and discharging for 2 times, and performing third charging when the charging amount is the actual maximum embedding PF of the positive electrode6 -At 10% of the capacity, the charging was stopped.
Fresh pre-embedded potassium ion cathode: KPF at 0.6mol/L6In the propylene carbonate electrolyte, the cathode plate obtained in the example 1 is separated from the metal potassium by adopting glass fiberThe membrane, constituting a half-cell. Discharging the half-cell on a charge-discharge instrument by adopting 0.02C multiplying current so as to pre-embed K+When pre-embedding K+The amount of (A) is that of the maximum practical insertion K of the negative electrode+When the capacity is 30%, the discharge is stopped.
All-battery: PF pre-intercalating the above anion6 -The positive electrode and the prepared fresh pre-embedded potassium ion negative electrode form a full battery, a glass fiber diaphragm is adopted, and the electrolyte is KPF with 0.6mol/L6Propylene carbonate.
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery reaches 98.1%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 98.5%.
Example 7:
the difference from example 1 is that the electrolyte in example 1 is replaced by NaClO4The electrolyte with the concentration of 1mol/L, the solvent in the electrolyte is a mixed solvent of ethylene carbonate and dimethyl carbonate, metal sodium is used as a reference electrode, and a diaphragm between a positive electrode and the metal sodium is a glass fiber diaphragm to form the half cell. Charging the half-cell with 0.1C multiplying current on a charging and discharging instrument, wherein the anion ClO4 -Starting to embed into the positive electrode, discharging after reaching the upper limit voltage, continuously charging and discharging for 2 times, and performing third charging when the charging amount is the maximum practical embedded ClO of the positive electrode4 -At 10% of the capacity, the charging was stopped.
Fresh pre-intercalation of sodium ion negative electrode: at 1mol/L of NaClO4In the electrolyte (mixed solvent of ethylene carbonate and dimethyl carbonate), the negative electrode sheet obtained in example 1 was used, and a glass fiber separator was used between the negative electrode sheet and sodium metal to form a half cell. Discharging the half-cell on a charge-discharge instrument by adopting current with 0.02C multiplying power so as to pre-embed Na+When pre-embedding Na+The amount of (A) is that the negative electrode can practically embed Na maximally+When the capacity is 30%, the discharge is stopped.
All-battery: the pre-embedded anions are ClO4 -The positive electrode and the prepared fresh pre-embedded sodium ion negative electrode form a full battery,adopts a glass fiber diaphragm and has 1mol/L of NaClO electrolyte4/(ethylene carbonate + dimethyl carbonate mixed solvent)
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery reaches 98.1%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 97.9%.
Example 8:
the difference from the embodiment 1 is that the electrolyte in the embodiment 1 is replaced by the electrolyte with the NaTFSI concentration of 0.7mol/L, the solvent in the electrolyte is 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide, the metal sodium is used as a reference electrode, and the diaphragm between the positive electrode and the metal sodium is a glass fiber diaphragm, so that the half cell is formed. Charging the half-cell with 0.1C multiplying current on the charging and discharging instrument, wherein the anion TFSI is adopted-Starting to embed into the positive electrode, discharging after reaching the upper limit voltage, continuously charging and discharging for 2 times, and performing third charging when the charging amount is the actual maximum embedded TFSI of the positive electrode-At 10% of the capacity, the charging was stopped.
Fresh pre-intercalation of sodium ion negative electrode: the negative electrode sheet obtained in the above example 1 was used in 0.7mol/L NaTFSI/1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide electrolyte, and a glass fiber separator was used between the negative electrode sheet and sodium metal to form a half cell. Discharging the half-cell on a charge-discharge instrument by adopting current with 0.02C multiplying power so as to pre-embed Na+When pre-embedding Na+The amount of (A) is that the negative electrode can practically embed Na maximally+When the capacity is 30%, the discharge is stopped.
All-battery: pre-intercalating the anion TFSI-The positive electrode and a fresh pre-embedded sodium ion negative electrode form a full cell, a glass fiber diaphragm is adopted, and the electrolyte is 0.7mol/L of NaTFSI/1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide.
And (4) measuring the obtained full battery, and continuously charging and discharging by adopting 2C multiplying current. As a result, it was found that: the first coulombic efficiency of the full battery reaches 98.5%, and after 3000 times of continuous charge and discharge, the capacity retention rate reaches 98.3%.
The above-mentioned embodiments only represent some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A full battery characterized in that: the anode is formed by pre-embedded anions and a fresh pre-embedded cations cathode in electrolyte through a diaphragm;
the pre-embedded anion positive electrode is a half-cell formed by a positive electrode and placed in electrolyte, charging is carried out through an external power supply, the charging rate current is 0.01C-0.2C, and the charging amount is 1-30% of the actual maximum embedded anion capacity of the positive electrode.
2. Full cell according to claim 1, characterized in that: the charging through the external power supply is carried out for one time until the actual maximum embedded anion capacity of the anode is reached; or, the negative ion-inserting capacity is increased to the actual maximum negative ion-inserting capacity after repeated continuous charging and discharging.
3. A full cell according to claim 2, wherein: the number of repeated continuous charging and discharging is 1-3.
4. A full cell according to claim 1, wherein: the half cell formed by the anode sequentially consists of a metal electrode, a diaphragm and the anode; wherein the metal electrode is lithium, sodium, potassium, aluminum, magnesium or zinc.
5. A full cell according to claim 1, wherein: the electrolyte consists of anions, cations and a solvent, wherein the anions are hexafluorophosphate PF6Hexafluoroarsenate AsF6Hexafluoroantimonate SbF6Tetra-fluoroborate BF4Bioxalic acid borate BOB-, DFOB-, TFSI-, FSI-, FAP-, CF-, etc3SO3- [ perchlorate ] ClO4-one of them;
the cation in the electrolyte is Li+、Na+、K+、Al3+、Mg2+、Zn2+One of (1);
the solvent in the electrolyte is Sulfolane (SL), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Propylene Carbonate (PC), Ethylene Carbonate (EC), Methyl Propyl Carbonate (MPC), gamma-butyrolactone (GBL), fluoroethylene carbonate (FEC), Ethyl Acetate (EA), trimethyl ethyl acetate (TMEA), Methyl Butyrate (MB), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Propyl Acetate (PA), Methyl Acetate (MA), ethyl acetoacetate (EAA), trimethyl methyl acetate, 1-butyl-1-methyl pyrrolidine bis (trifluoromethanesulfonyl) imide (Pyr)14TFSI);
the concentration of the electrolyte is 0.1-5 mol/L.
6. Full cell according to claim 1, characterized in that: the manufacturing method of the positive and negative pole pieces comprises the steps of mixing an active material, a conductive agent and a binder into slurry according to the mass ratio of 90: 1-5: 1:5, coating the positive pole on an aluminum foil, coating the negative pole on a copper foil, keeping the mixture in a vacuum oven at 120 ℃ for 24 hours, and cutting the mixture into fixed shapes.
7. Full cell according to claim 1, characterized in that: a fresh positive ion pre-intercalation negative electrode is obtained by forming a circuit by the negative electrode obtained in claim 6 and a lithium metal sheet, and intercalating lithium into the negative electrode by using a current of 0.02C, wherein the capacity of the negative electrode pre-intercalation lithium accounts for 20-50% of the actual maximum intercalation lithium capacity of the negative electrode active material.
8. Full cell according to claim 6, characterized in that: the positive and negative electrode active materials are graphite materials; the binder is one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), hydroxypropyl methylcellulose (HPMC), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); the conductive agent is one or more of carbon black, graphite, graphitized carbon fiber and carbon nano tube.
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